Synthesis and Characterization of SPIONs Encapsulating Polydopamine Nanoparticles and Their Test for Aqueous Cu2+ Ion Removal.

The removal of pollutants, such as heavy metals, aromatic compounds, dyes, pesticides and pharmaceuticals, from water is still an open challenge. Many methods have been developed and exploited for the purification of water from contaminants, including photocatalytic degradation, biological treatment, adsorption and chemical precipitation. Absorption-based techniques are still considered among the most efficient and commonly used approaches thanks to their operational simplicity. In recent years, polydopamine-coated magnetic nanoparticles have emerged for the uptake of heavy metals in water treatment, since they combine specific affinity towards pollutants and magnetic separation capacity. In this context, this work focuses on the synthesis of polydopamine (PDA)-coated Super Paramagnetic Iron Oxide Nanoparticles (PDA@SPIONs) as adsorbents for Cu2+ ions, designed to serve as functional nanostructures for the removal of Cu2+ from water by applying a magnetic field. The synthetic parameters, including the amount of SPIONs and PDA, were thoroughly investigated to define their effects on the nanostructure features and properties. Subsequently, the ability of the magnetic nanostructures to bind metal ions was assessed on Cu2+-containing solutions. A systematic investigation of the prepared functional nanostructures was carried out by means of complementary spectroscopic, morphological and magnetic techniques. Inductively coupled plasma atomic emission spectroscopy (ICP-AES) measurements were performed in order to estimate the Cu2+ binding ability. The overall results indicate that these nanostructures hold great promise for future bioremediation applications.

Gold nanoparticles modified graphene platforms for highly sensitive electrochemical detection of vitamin C in infant food and formulae.

An easy and reliable method based on a novel electroanalytical nanostructured sensor has been developed to perform quantification of vitamin C in commercial and fortified cow-milk-based formulae and foods for infants and young children. The work is motivated by the need of a reliable analytical tool to be applied in quality control laboratories for the quantitative assessment of vitamin C where its rapid and cost-effective monitoring is essential. The ad hoc designed sensor, based on disposable screen-printed carbon electrodes modified with Au nanoparticles decorated reduced graphene oxide flakes, exhibits a LOD of 0.088 mg L-1. The low cost, easy sample preparation, fast response and high reproducibility (RSD ≈ 8%) of the proposed method highlight its suitability for usage in quality control laboratories for determining vitamin C in real complex food matrices, envisaging the application of the sensing platform in the determination of other compounds relevant in food chemistry and food manufacturing.

Gold-Speckled SPION@SiO2 Nanoparticles Decorated with Thiocarbohydrates for ASGPR1 Targeting: Towards HCC Dual Mode Imaging Potential Applications.

Efforts are made to perform an early and accurate detection of hepatocellular carcinoma (HCC) by simultaneous exploiting multiple clinically non-invasive imaging modalities. Original nanostructures derived from the combination of different inorganic domains can be used as efficient contrast agents in multimodal imaging. Superparamagnetic iron oxide nanoparticles (SPIONs) and Au nanoparticles (NPs) possess well-established contrasting features in magnetic resonance imaging (MRI) and X-ray computed tomography (CT), respectively. HCC can be targeted by using specific carbohydrates able to recognize asialoglycoprotein receptor 1 (ASGPR1) overexpressed in hepatocytes. Here, two different thiocarbohydrate ligands were purposely designed and alternatively conjugated to the surface of Au-speckled silica-coated SPIONs NPs, to achieve two original nanostructures that could be potentially used for dual mode targeted imaging of HCC. The results indicated that the two thiocarbohydrate decorated nanostructures possess convenient plasmonic/superparamagnetic properties, well-controlled size and morphology and good selectivity for targeting ASGPR1 receptor.

Stimuli-responsive nanoparticle-assisted immunotherapy: a new weapon against solid tumours.

Although significant improvements in cancer treatment have led to a longer survival period, the death rate of patients with solid tumours has not changed during the last decades. Most researchers are currently concentrating on defining the mechanisms of the different resistance pathways activated by tumour cells; meanwhile, the role of limited drug distribution within tumours has been neglected. The application of nanotechnology in medicine offers unexplored opportunities for realizing a new generation of anticancer therapies that can overcome the physical hindrances that characterize solid tumours. Indeed, surface-engineered nanoparticles (NPs) (both organic and inorganic) have been used as powerful tools in cancer therapy. Particularly, Au NPs have been utilized to develop a new drug-free treatment, photo-thermal therapy (PTT), due to their stimuli-responsive properties. PTT combined with immunotherapy represents a major breakthrough in the fight against malignant solid tumours. In this review, we provide a complete overview of the synergistic approaches based on PTT and immunotherapy, considering the selection, design, and functionalization of the NPs and their thermo-optical properties, moving to in vivo studies and finally to clinical trial applications in patients suffering from solid tumours.

Scalable Synthesis of Mesoporous TiO2 for Environmental Photocatalytic Applications.

Increasing environmental concern, related to pollution and clean energy demand, have urged the development of new smart solutions profiting from nanotechnology, including the renowned nanomaterial-assisted photocatalytic degradation of pollutants. In this framework, increasing efforts are devoted to the development of TiO2-based nanomaterials with improved photocatalytic activity. A plethora of synthesis routes to obtain high quality TiO2-based nanomaterials is currently available. Nonetheless, large-scale production and the application of nanosized TiO2 is still hampered by technological issues and the high cost related to the capability to obtain TiO2 nanoparticles with high reaction yield and adequate morphological and structural control. The present review aims at providing a selection of synthetic approaches suitable for large-scale production of mesoporous TiO2-based photocatalysts due to its unique features including high specific surface area, improved ultraviolet (UV) radiation absorption, high density of surface hydroxyl groups, and significant ability for further surface functionalization The overviewed synthetic strategies have been selected and classified according to the following criteria (i) high reaction yield, (ii) reliable synthesis scale-up and (iii) adequate control over morphological, structural and textural features. Potential environmental applications of such nanostructures including water remediation and air purification are also discussed.

Green Fluorescent Terbium (III) Complex Doped Silica Nanoparticles.

The low photostability of conventional organic dyes and the toxicity of cadmium-based luminescent quantum dots have prompted the development of novel probes for in vitro and in vivo labelling. Here, a new fluorescent lanthanide probe based on silica nanoparticles is fabricated and investigated for optically traceable in vitro translocator protein (TSPO) targeting. The targeting and detection of TSPO receptor, overexpressed in several pathological states, including neurodegenerative diseases and cancers, may provide valuable information for the early diagnosis and therapy of human disorders. Green fluorescent terbium(III)-calix[4]arene derivative complexes are encapsulated within silica nanoparticles and surface functionalized amine groups are conjugated with selective TSPO ligands based on a 2-phenylimidazo[1,2-a]pyridine acetamide structure containing derivatizable carboxylic groups. The photophysical properties of the terbium complex, promising for biological labelling, are demonstrated to be successfully conveyed to the realized nanoarchitectures. In addition, the high degree of biocompatibility, assessed by cell viability assay and the selectivity towards TSPO mitochondrial membrane receptors, proven by subcellular fractional studies, highlight targeting potential of this nanostructure for in vitro labelling of mitochondria.

Au nanoparticle in situ decorated RGO nanocomposites for highly sensitive electrochemical genosensors.

A novel hybrid nanocomposite formed by RGO flakes, surface functionalized by 1-pyrene carboxylic acid (PCA), densely and uniformly in situ decorated by Au NPs, that are concomitantly coordinated by the PCA carboxylic group, and by an aromatic thiol used as the reducing agent in the synthesis, both ensuring, at the same time, a stable non-covalent NPs anchorage to the RGO flakes, and an efficient interparticle electron coupling along the NP network onto the RGO, is reported. The obtained solution processable hybrid material is used to modify Screen-Printed Carbon Electrodes (SPCEs). The hybrid modified SPCEs, functionalized with a thiolated DNA capture probe, are tested in a streptavidin-alkaline-phosphatase catalyzed assay, for the detection of the biotinylated miRNA-221, and for its determination in spiked human blood serum samples. The proposed genosensor demonstrates a high sensitivity (LOD of 0.7 pM), attesting for a performance comparable with the most effective reported sensors. The enhanced sensitivity is explained in terms of the very fast heterogeneous electron transfer kinetics, the concomitant decrease of the electron transfer resistance at the electrode/electrolyte interface, the high electroactivity and the high surface area of the nanostructured hybrid modified SPCEs that provide a convenient platform for nucleic acid biosensing.

Surface Engineering of Gold Nanorods for Cytochrome c Bioconjugation: An Effective Strategy To Preserve the Protein Structure.

The surface of gold nanorods (Au NRs) has been appropriately engineered to achieve a suitable interface for bioconjugation with horse heart cytochrome c (HCc). HCc, an extensively studied and well-characterized protein, represents an ideal model for nanoparticle (NP)-protein conjugation studies because of its small size, high stability, and commercial availability. Here, the native state of the protein has been demonstrated for the first time, by means of Raman spectroscopy, to be retained upon conjugation with the anisotropic Au nanostructures, thus validating the proposed protocol as specifically suited to mostly preserve the plasmonic properties of the NRs and to retain the structure of the protein. The successful creation of such bioconjugates with the retention of the protein structure and function along with the preservation of the NP properties represents a challenging but essential task, as it provides the only way to access functional hybrid systems with potential applications in biotechnology, medicine, and catalysis. In this perspective, the organic capping surrounding the Au NRs plays a key role, as it represents the functional interface for the conjugation step. Cetyltrimethylammonium bromide-coated Au NRs, prepared by using a seed-mediated synthetic route, have been wrapped with polyacrylic acid (PAA) by means of electrostatic interactions following a layer-by-layer approach. The resulting water-dispersible negatively charged AuNRs@PAA NPs have then been electrostatically bound to the positively charged HCc. The bioconjugation procedure has been thoroughly monitored by the combined analysis of UV-vis absorption, resonance Raman and Fourier transform infrared spectroscopies, transmission electron microscopy microscopy, and ζ-potential, which verified the successful conjugation of the protein to the nanorods.

Spectroscopic Insights into Carbon Dot Systems.

The controversial nature of the fluorescent properties of carbon dots (CDs), ascribed either to surface states or to small molecules adsorbed onto the carbon nanostructures, is an unresolved issue. To date, an accurate picture of CDs and an exhaustive structure-property correlation are still lacking. Using two unconventional spectroscopic techniques, fluorescence correlation spectroscopy (FCS) and time-resolved electron paramagnetic resonance (TREPR), we contribute to fill this gap. Although electron micrographs indicate the presence of carbon cores, FCS reveals that the emission properties of CDs are based neither on those cores nor on molecular species linked to them, but rather on free molecules. TREPR provides deeper insights into the structure of carbon cores, where C sp2 domains are embedded within C sp3 scaffolds. FCS and TREPR prove to be powerful techniques, characterizing CDs as inherently heterogeneous systems, providing insights into the nature of such systems and paving the way to standardization of these nanomaterials.

Fabrication of photoactive heterostructures based on quantum dots decorated with Au nanoparticles.

Silica based multifunctional heterostructures, exhibiting near infrared (NIR) absorption (650-1200 nm) and luminescence in the visible region, represent innovative nanosystems useful for diagnostic or theranostic applications. Herein, colloidal synthetic procedures are applied to design a photoactive multifunctional nanosystem. Luminescent silica (SiO2) coated quantum dots (QDs) have been used as versatile nanoplatforms to assemble on their surface gold (Au) seeds, further grown into Au spackled structures. The synthesized nanostructures combine the QD emission in the visible region, and, concomitantly, the distinctive NIR absorption of Au nanodomains. The possibility of having multiple QDs in a single heterostructure, the SiO2 shell thickness, and the extent of Au deposition onto SiO2 surface have been carefully controlled. The work shows that a single QD entrapped in 16 nm thick SiO2 shell, coated with Au speckles, represents the most suitable geometry to preserve the QD emission in the visible region and to generate NIR absorption from metal NPs. The resulting architectures present a biomedical potential as an effective optical multimodal probes and as promising therapeutic agents due to the Au NP mediated photothermal effect.

Cytotoxicity Study on Luminescent Nanocrystals Containing Phospholipid Micelles in Primary Cultures of Rat Astrocytes.

Luminescent colloidal nanocrystals (NCs) are emerging as a new tool in neuroscience field, representing superior optical probes for cellular imaging and medical diagnosis of neurological disorders with respect to organic fluorophores. However, only a limited number of studies have, so far, explored NC applications in primary neurons, glia and related cells. Indeed astrocytes, as resident cells in the central nervous system (CNS), play an important pathogenic role in several neurodegenerative and neuroinflammatory diseases, therefore enhanced imaging tools for their thorough investigation are strongly amenable. Here, a comprehensive and systematic study on the in vitro toxicological effect of core-shell type luminescent CdSe@ZnS NCs incorporated in polyethylene glycol (PEG) terminated phospholipid micelles on primary cultures of rat astrocytes was carried out. Cytotoxicity response of empty micelles based on PEG modified phospholipids was compared to that of their NC containing counterpart, in order to investigate the effect on cell viability of both inorganic NCs and micelles protecting NC surface. Furthermore, since the surface charge and chemistry influence cell interaction and toxicity, effect of two different functional groups terminating PEG-modified phospholipid micelles, namely amine and carboxyl group, respectively, was evaluated against bare micelles, showing that carboxyl group was less toxic. The ability of PEG-lipid micelles to be internalized into the cells was qualitatively and quantitatively assessed by fluorescence microscopy and photoluminescence (PL) assay. The results of the experiments clearly demonstrate that, once incorporated into the micelles, a low, not toxic, concentration of NCs is sufficient to be distinctly detected within cells. The overall study provides essential indications to define the optimal experimental conditions to effectively and profitably use the proposed luminescent colloidal NCs as optical probe for future in vivo experiments.

UV-curable nanocomposite based on methacrylic-siloxane resin and surface-modified TiO2 nanocrystals.

A novel UV-light-curable nanocomposite material formed of a methacrylic-siloxane resin loaded with 1 wt % oleic acid and 3-(trimethoxysilyl)propyl methacrylate silane (OLEA/MEMO)-coated TiO2 nanorods (NRs) has been manufactured as a potential self-curing structural coating material for protection of monuments and artworks, optical elements, and dental components. OLEA-coated TiO2 NRs, presynthesized by a colloidal chemistry route, have been surface-modified by a treatment with the methacrylic-based silane coupling agent MEMO. The resulting OLEA/MEMO-capped TiO2 NRs have been dispersed in MEMO; that is a monomer precursor of the organic formulation, used as a "common solvent" for transferring the NRs in prepolymer components of the formulation. Differential scanning calorimetry and Fourier transform infrared spectroscopy have allowed investigation of the effects of the incorporation of the OLEA/MEMO-capped TiO2 NRs on reactivity and photopolymerization kinetics of the nanocomposite, demonstrating that the embedded NRs significantly increase curing reactivity of the neat organic formulation both in air and inert atmosphere. Such a result has been explained on the basis of the photoactivity of the nanocrystalline TiO2 which behaves as a free-radical donor photocatalyst in the curing reaction, finally turning out more effective than the commonly used commercial photoinitiator. Namely, the NRs have been found to accelerate the cure rate and increase cross-linking density, promoting multiple covalent bonds between the resin prepolymers and the NR ligand molecules, and, moreover, they limit inhibition effect of oxygen on photopolymerization. The NRs distribute uniformly in the photocurable matrix, as assessed by transmission electron microscopy analysis, and increase glass transition temperature and water contact angle of the nanocomposite with respect to the neat resin.

Photoactive hybrid material based on pyrene functionalized PbS nanocrystals decorating CVD monolayer graphene.

A simple and facile solution-based procedure is implemented for decorating a large area, monolayer graphene film, grown by chemical vapor deposition, with size-tunable light absorbing colloidal PbS nanocrystals (NCs). The hybrid is obtained by exposing a large area graphene film to a solution of 1-pyrene butyric acid surface coated PbS NCs, obtained by a capping exchange procedure onto presynthesized organic-capped NCs. The results demonstrate that at the interface, multiple and cooperative π-π stacking interactions promoted by the pyrene ligand coordinating the NC surface lead to a successful anchoring of the nano-objects on the graphene platform which concomitantly preserves its aromatic structure. Interligand interactions provide organization of the nano-objects in highly interconnected nanostructured multilayer coatings, where the NCs retain geometry and composition. The resulting hybrid exhibits a sheet resistance lower than that of bare graphene, which is explained in terms of electronic communication in the hybrid, due to the interconnection of the NC film and to a hole transfer from photoexcited PbS NCs to graphene, channelled at the interface by pyrene. Such a direct electron coupling makes the manufactured hybrid material an interesting component for optoelectronics, sensors and for optical communication and information technology.

Tuning light emission of PbS nanocrystals from infrared to visible range by cation exchange.

Colloidal semiconductor nanocrystals, with intense and sharp-line emission between red and near-infrared spectral regions, are of great interest for optoelectronic and bio-imaging applications. The growth of an inorganic passivation layer on nanocrystal surfaces is a common strategy to improve their chemical and optical stability and their photoluminescence quantum yield. In particular, cation exchange is a suitable approach for shell growth at the expense of the nanocrystal core size. Here, the cation exchange process is used to promote the formation of a CdS passivation layer on the surface of very small PbS nanocrystals (2.3 nm in diameter), blue shifting their optical spectra and yielding luminescent and stable nanostructures emitting in the range of 700-850 nm. Structural, morphological and compositional investigation confirms the nanocrystal size contraction after the cation-exchange process, while the PbS rock-salt crystalline phase is retained. Absorption and photoluminescence spectroscopy demonstrate the growth of a passivation layer with a decrease of the PbS core size, as inferred by the blue-shift of the excitonic peaks. The surface passivation strongly increases the photoluminescence intensity and the excited state lifetime. In addition, the nanocrystals reveal increased stability against oxidation over time. Thanks to their absorption and emission spectral range and the slow recombination dynamics, such highly luminescent nano-objects can find interesting applications in sensitized photovoltaic cells and light-emitting devices.

Optical and conductive properties of as-synthesized organic-capped TiO2 nanorods highly dispersible in polystyrene-block-poly(methyl methacrylate) diblock copolymer.

As-synthesized organic-capped TiO2 nanorods were incorporated into polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymer to achieve TiO2/PS-b-PMMA nanocomposites with enhanced optical and conductive properties. The specific surface chemistry of TiO2 nanorods derived from the colloidal synthetic approach allowed their prompt incorporation in the PS-b-PMMA block copolymer template up to 50 wt %, which resulted in films with an extended coverage of highly dispersed nanoparticles for contents higher than 30 wt %. At such high nanorod contents, the films fabricated by the prepared nanocomposites demonstrated enhanced optical properties. Atomic force microscopy investigation of the nanocomposite films showed a cylindrical morphology for low nanorod contents. Conversely, higher nanorod contents resulted upon removal of the organic component in the nanocomposites with UV treatment in overall nanorod coverage of the film surface with the concomitant formation of charge percolation paths, which led to noticeable conductivity values. EFM and PF-TUNA measurements confirmed the conductive properties of the composites at nanoscale, whereas semiconductor analyzer measurements provided their macroscale characterization. In addition, an increase in the UV-vis absorption was observed with the increase in the nanorod content along with a remarkable conductivity of the overall film.

Selective confinement of oleylamine capped Au nanoparticles in self-assembled PS-b-PEO diblock copolymer templates.

Amphiphilic polystyrene-block-polyethylene oxide (PS-b-PEO) block copolymers (BCPs) have been demonstrated to be effective in directing organization of colloidal Au nanoparticles (NPs). Au NPs have been incorporated into the polymer and the different chemical affinity between the NP surface and the two blocks of the BCP has been used as a driving force of the assembling procedure. The morphology of the nanocomposites, prepared and fabricated as thin films, has been investigated by means of atomic force and scanning electron microscopies as a function of the NP content and BCP molecular weight. NPs have been effectively dispersed in PS-b-PEO hosts at any investigated content (up to 17 wt%) and a clear effect of the BCP properties on the final nanocomposite morphology has been highlighted. Finally, electrostatic force microscopy has demonstrated the conductive properties of the nanocomposite films, showing that the embedded Au NPs effectively convey their conductive properties to the film. The overall investigation has confirmed the selective confinement of the as-prepared surfactant-coated metal NPs in the PS block of PS-b-PEO, thus proposing a very simple and prompt assembling tool for nanopatterning, potentially suitable for optoelectronic, sensing and catalysis applications.

Three-dimensional self-assembly of networked branched TiO2 nanocrystal scaffolds for efficient room-temperature processed depleted bulk heterojunction solar cells.

In this work, we report on ∼4% power conversion efficiency (PCE) depleted bulk heterojunction (DBH) solar cells based on a high-quality electrode with a three-dimensional nanoscale architecture purposely designed so as to maximize light absorption and charge collection. The newly conceived architecture comprises a mesoporous electron-collecting film made of networked anisotropic metal-oxide nanostructures, which accommodates visible-to-infrared light harvesting quantum dots within the recessed regions of its volume. The three-dimensional electrodes were self-assembled by spin-coating a solution of colloidal branched anatase TiO2 NCs (BNC), followed by photocatalytic removal of the native organic capping from their surface by a mild UV-light treatment and filling with small PbS NCs via infiltration. The PCE ∼ 4% of our TiO2 BNC/PbS QD DBH solar cell features an enhancement of 84% over the performance obtained for a planar device fabricated under the same conditions. Overall, the DBH device fabrication procedure is entirely carried out under mild processing conditions at room temperature, thus holding promise for low-cost and large-scale manufacturing.

Electroactive layer-by-layer plasmonic architectures based on Au nanorods.

Nanostructured films based on Au nanorods (NRs) have been obtained by layer-by-layer (LbL) assembly driven by electrostatic interaction between metal nanoparticles and polyelectrolytes. Multilayer films have been fabricated by using LbL assembly of poly(sodium styrenesulfonate) (PSS) and positively charged Au NRs on a polyelectrolyte-modified substrate. The effect of fabrication parameters, including the nature of the substrate, the polyelectrolyte initial anchoring layer, and the number of layers has been investigated by means of UV-vis absorbance spectroscopy and atomic force microscopy (AFM). The results demonstrated the dependence of morphology and plasmonic features in the multilayered nanostructured architectures from the nature of the anchoring polyelectrolyte on the substrate, the number of layers, and the kind of NR mutual assembly. In addition, a study of the electrochemical activity at the solid/liquid interface has been carried out in order to assess charge transport through the NR multilayer by using two molecular probes in solution, namely, potassium ferricyanide, a common and well-established redox mediator with reversible behavior, and cytochrome C, a robust model redox protein. The presented systematic study of the immobilization of Au NRs opens the venue to several application areas, such as (bio)chemical sensing.

Plasmon mediated super-absorber flexible nanocomposites for metamaterials.

A flexible host has been selected to achieve, for the first time, functional nanocomposites based on CdSe@ZnS core-shell type quantum dots (QDs) and Au nanoparticles (NPs), simultaneously dispersed in a polymer matrix. Coherent interactions between QDs and plasmonic Au NPs embedded in PDMS films have been demonstrated to lead to a relevant enhancement of the absorption cross-section of the QDs, remarkably modifying the optical response of the entire system. Optical and time resolved spectroscopy studies revealed an active gain-plasmon feedback behind the super-absorbing overall effect.

A combined size sorting strategy for monodisperse plasmonic nanostructures.

The fabrication of highly monodisperse silica coated Au NPs by the microemulsion approach and the selection of the nanostructure morphology have been described. Several experimental conditions, synthetic parameters and post-preparative strategies such as reaction time, precursor concentration, size selection techniques and NP surface treatments have been suitably investigated in order to fabricate Au and Au@SiO2 NPs with peculiar and tuneable plasmonic properties that strongly depend on the specific size distribution and nanostructure morphology. In particular, size selected precipitation of oleylamine-capped Au NPs by antisolvent titration has successfully offered a strategy to discriminate and collect monodisperse fractions with different average size and narrow size distribution. Moreover, for the first time, a deep insight into the microemulsion mechanism for the silica shell growth has been provided, highlighting the critical role played by the density of oleylamine at the Au NP surface. Specifically the capping agent has been demonstrated to strongly determine the multiplicity of the core in the final Au@SiO2 nanostructures. Density gradient centrifugation has been finally performed to sort the achieved Au@SiO2 NPs with different morphologies, which was ultimately able to recover a significant fraction formed of two Au NPs in one silica shell. A systematic characterization of the Au and Au@SiO2 NPs has been carried out by complementary morphological and spectroscopic techniques. These deeply investigated materials, with tuneable plasmonic properties, have been proposed as versatile building blocks useful for the design and fabrication of plasmonic and photonic structures as well as metamaterials for device applications.